TY - JOUR

T1 - Comparative study of physico-chemical properties of tetraalkylammonium perchlorates and composites on their basis

AU - Stebnitskii, Ivan

AU - Mateyshina, Yulia

AU - Uvarov, Nikolai

N1 - This research was funded by the Russian Science Foundation, project 20–13-00302.

PY - 2025/3/22

Y1 - 2025/3/22

N2 - The effect of the cation in pure salts (n-CyH2y+1)4ClO4 (y = 3, 4) and in composites based on them with highly dispersed nanodiamonds (specific surface area 300 ± 20 m2/g) has been studied using X-ray diffraction analysis (including high-temperature X-ray diffraction analysis), differential scanning calorimetry and impedance spectroscopy. Pure salts undergo 2 (n-C3H7)4ClO4 at 173 ºC and 178 ºC) or 1 (n-C4H9)4ClO4 at 60 ºC) solid–solid phase transitions. Both salts undergo polymorphic transformations to a disordered weakly conducting cubic phase with the space group P4¯3n. The addition of nanodiamonds leads to a significant decrease in the enthalpies of phase transformations and intensities of reflections, which is associated with the formation of amorphous phases with a thickness of about 2 nm. The introduction of nanodiamonds leads to a significant increase in conductivity compared to the original compounds. The maximum conductivity values were achieved for the compositions 0.02(n-C3H7)4NClO4–0.98CND (4.9 × 10–4 S/cm at 165 ⁰C) and 0.015(n-C4H9)4NClO4–0.985CND (7.1 × 10–4 S/cm at 165 ⁰C), which is associated with the formation of a highly conductive amorphous phase, whose conductivity is 3–4 orders of magnitude higher than that of the original salts.

AB - The effect of the cation in pure salts (n-CyH2y+1)4ClO4 (y = 3, 4) and in composites based on them with highly dispersed nanodiamonds (specific surface area 300 ± 20 m2/g) has been studied using X-ray diffraction analysis (including high-temperature X-ray diffraction analysis), differential scanning calorimetry and impedance spectroscopy. Pure salts undergo 2 (n-C3H7)4ClO4 at 173 ºC and 178 ºC) or 1 (n-C4H9)4ClO4 at 60 ºC) solid–solid phase transitions. Both salts undergo polymorphic transformations to a disordered weakly conducting cubic phase with the space group P4¯3n. The addition of nanodiamonds leads to a significant decrease in the enthalpies of phase transformations and intensities of reflections, which is associated with the formation of amorphous phases with a thickness of about 2 nm. The introduction of nanodiamonds leads to a significant increase in conductivity compared to the original compounds. The maximum conductivity values were achieved for the compositions 0.02(n-C3H7)4NClO4–0.98CND (4.9 × 10–4 S/cm at 165 ⁰C) and 0.015(n-C4H9)4NClO4–0.985CND (7.1 × 10–4 S/cm at 165 ⁰C), which is associated with the formation of a highly conductive amorphous phase, whose conductivity is 3–4 orders of magnitude higher than that of the original salts.

KW - Ionic conductivity

KW - Nanodiamonds

KW - Organic ionic plastic crystals

KW - Tetrabutylammonium perchlorate

KW - Tetrapropylammonium perchlorate

UR - https://www.mendeley.com/catalogue/36be6c7e-9e4d-3646-afa0-e7c58fa74024/

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-105000551527&origin=inward&txGid=0d60db036fb37b03932d2f86276d0ff1

U2 - 10.1007/s11581-025-06243-y

DO - 10.1007/s11581-025-06243-y

M3 - Article

JO - Ionics

JF - Ionics

SN - 0947-7047

M1 - 116419

ER -